Novel metal-diketone absorbents for carbon monoxide or olefins

ABSTRACT

Novel compounds for absorbing carbon monoxide and olefinically-unsaturated compounds from feedstreams are of the formula ##STR1## wherein R 1  is trichloromethyl or R F  ; R F  is C n  F 2n+1  and n is 1-8; R 2  is H or hydrocarbyl of 2-20 carbon atoms having at least one olefinic unsaturated bond; M I  is Cu I  or Ag I  and R 3  is hydrocarbyl of 2-20 carbon atoms having at least one olefinic unsaturated bond.

This is a division of application Ser. No. 083,742, filed Aug. 7, 1987,now abandoned.

TECHNICAL FIELD

This invention relates to novel metal-containing complexes, whichselectively absorb carbon monoxide or olefinically-unsaturated compoundsfrom feedstreams.

BACKGROUND ART

Carbon monoxide is produced in a variety of incomplete oxidationprocesses. It appears in refinery off gas, methanol plant purge gas,blast furnace gas, water gas, coke oven gas and the gaseous effluent ofsteam reforming of methane. It would be highly desirable to isolate anduse this carbon monoxide as a feedstock for other processes, forexample, in making acetic acid. Methods for separating carbon monoxidefrom gas mixtures have been developed, including cryogenic distillationmethods. These procedures are expensive. Therefore, there is a need foreconomical chemical processes for removing carbon monoxide from feedstreams and recovering relatively pure carbon monoxide at the end of theseparation process. Chemical separation processes are accordingly basedon reversible binding of carbon monoxide with an absorbent, which willrelease carbon monoxide under appropriate conditions.

The separation of olefins from other hydrocarbons, including saturatedhydrocarbons and aromatic hydrocarbons, is also of commercial interest.Although this can be accomplished by distillation, there is considerableinterest in chemical processes, depending on selective complexation ofone of a mixture of unsaturated hydrocarbons with an absorbent, whichwill release the hydrocarbon of interest under selected conditions.

The use of various metallic complexes has been investigated for theseparation of both carbon monoxide and olefins from feed streams.

Doyle (U.S. Pat. No. 4,385,005) has proposed the use of a mixture ofcopper(I) or silver(I) oxide and a perfluorinated acetylacetonate toremove unsaturated hydrocarbons from feedstreams.

Carbon monoxide and alkene derivatives of copper(I) and silver(I)betadiketonates have been reported by Doyle et al., Organometallics,vol. 4 (1985), pages 830-835. These complexes are of varying stabilitywith respect to air oxidation and disproportionation, but areinsensitive to moisture.

Doyle has proposed in U.S. Pat. No. 4,279,874, using Cu(I) halogenatedacetylacetonate complexes for the separation of carbon monoxide from agas stream.

The use of Cu(I) complexes of fluorinated acetylacetone in an organicsolvent for the removal of unaturated hydrocarbons from feedstreams hasbeen proposed by Doyle et al. in U.S. Pat. Nos. 4,434,317 and 4,508,694.The use of a stabilized cuprous fluorinated acetonylacetonate isproposed by Doyle et al. in U.S. Pat. No. 4,471,152.

Long et al. (U.S. Pat. No. 3,592,865) have recited using cuprousaluminum halide complexes to remove complexible ligands fromfeedstreams.

Walker, "Making and using CO," Chemtech (May, 1975), pages 308-311, hasdescribed the Cosorb purification process for separating carbon monoxidefrom gaseous mixtures, including streams rich in nitrogen. The processrelies on stabilization of the active component, cuproustetrachloroaluminate, in an aromatic solvent.

Dunlop et al., in U.S. Pat. No. 3,401,112, have recited separatinghydrocarbons of various kinds of unsaturation using cuprous salts ofoxyacids.

References suggesting the state of the art of metal complexes, usingorganic or inorganic copper(I) or silver(I) compounds, include:

M. Bertholet, "Observations Relatives a L'action des Sels Cuivreux surles Carbures D'hydrogene et sur L'oxyde de carbon," Ann. de Chim. et dePhys., 7th series, vol. XXIII (May, 1901), pages 32-39

M. I. Bruce, "Carbonyl Chemistry of the Group IB Metals," J.Organometal. Chem., vol. 44 (1972), pages 209-228

E. R. Gilliland et al., "Reactions of Olefins with Solid CuprousHalides," J. Am. Chem. Soc., vol. 61 (1939), pages 1960-1962; ibid.,vol. 63

(1941), pages 2088-2090

R. J. Hurtado et al., "Copper(I) Nitrile Complexes, Part III. ReversibleOlefin Complex Formation with Acetonitrilecopper(I)Trifluoromethanesulfonate," Transition Met. Chem., vol. 2 (1977), pages91-94

F. R. Hartley et al., "Influence of Solvent on the Stability ofSilver(I)-Olefin Complexes," J. Chem. Soc. Dalton (1977), pages 469-477

J. Liebig, "Ueber die Constitution des Aethers und seiner Verbindungen,"Ann. der Pharmacie, vol. IX (1834), pages 1-39; "Ueber dieAethertheorie, in besonderer Rucksicht auf die vorhergehende AbhandlungZeise's", ibid., vol. 23 (1837), pages 12-42

M. A. Lur'e et al., "Separation of 1,3-Butadiene from a Mixture of OtherHydrocarbons Using Cuprous Chloride," Sinet. Kauchuk, vol. 3, no. 6(1934), pages 19-29

S. Winstein et al., "The Coordination of Silver Ion with UnsaturatedCompounds," J. Am. Chem. Soc., vol. 60 (1938), pages 836-847.

Kamitori et al., Synthesis, April, 1986, pages 340-342, have recited thepreparation of 3-allyl-1,1,1-trifluoroacetylacetone and relatedcompounds, which are useful as chelating agents.

DISCLOSURE OF INVENTION

In one aspect, this invention relates to novel unsaturatedtrichloromethyl or perfluoroalkyl diketones of the formula ##STR2##wherein R₁ is trichloromethyl or R_(F) ; R_(F) is C_(n) F_(2n) +1 and nis 1-8; and R₃ is hydrocarbyl of 2-20 carbon atoms having at least oneolefinic unsaturated bond.

In another aspect, this invention relates to Cu^(I) or Ag^(I) complexesof perfluoroalkyl diketonate compounds, having the formula ##STR3##wherein R₁ and R₃ are as above, M^(I) is Cu^(I) or Ag^(I) and R₂ is H orhydrocarbyl of 2-20 carbon atoms having at least one olefinicunsaturated bond.

This invention further relates to a process for removing carbon monoxideor an unsaturated hydrocarbon containing at least one olefinicunsaturated bond from a feedstream by contacting the feedstream with ametal-diketonate compound, as above, in an inert organic solvent orvehicle.

In yet another aspect, this invention relates to compounds of theformula ##STR4## wherein R_(F') and R_(F") are independently selectedfrom perfluoroalkyl of 1-8-carbon atoms and R is hydrocarbyl of 2-20carbon atoms having at least one olefinic unsaturated bond.

This invention further relates to novel metal-diketone compounds of theformula ##STR5## wherein R_(F"), R_(F'"), and R and M^(I) are as above,as well as to their use as absorbents for carbon monoxide and olefins infeed streams.

In a further aspect, this invention relates to a process for makingcompounds of the formula ##STR6## wherein R₁, R₂ and R₃ are as above,comprising the steps of:

(a) treating a ketone of the formula R₂ CH₂ COR₃ with lithiumdiisopropylamide to produce a compound of the formula R₂ CHCOR₃ ⁻ Li⁺ ;and

(b) reacting thus-produced R₂ CHCOR₃ ⁻ Li⁺ with a compound of theformula R_(F) COOalk or CCl₃ COOalk, wherein R_(F) is as above and alkis alkyl of 1-6 carbon atoms, to produce the desired compound.

The trichloromethyl or perfluoroalkyl diketones of this invention canexist in two tautomeric forms, enol or ketone, corresponding to ##STR7##Alternatively, the tautomeric mixture can be represented by the formula##STR8##

The perfluoroalkyl or trichloromethyl diketones are made from anunsaturated ketone of the formula R₂ CH₂ COR₃, wherein R₂ and R₃ are asabove. This is converted to a lithio derivative, represented by theformula R₂ CHLiCOR₃ by reaction with lithium diisopropylamide underanhydrous conditions. The resulting anion ⁻ R₂ CHCOR₃ adds to thecarbonyl of R_(F) COOalk or CCl₃ COOalk to produce a beta-diketonate,which is protonated to the desired product, that is, to R₁ COCHR₂ COR₃.

Preferred diketone derivatives of this invention are those derived fromtrifluoroacetylacetone. It is therefore preferred to react a lithiatedunsaturated ketone with a trifluoroacetate ester, most preferably withethyl trifluoroacetate. It is preferred to carry out reactions in whichR₂ CCH₂ COR₃ is 5-hexen-2-one, 6-methyl-5-hepten-2-one, geranyl acetone,neryl acetone, 3-prenyl-2-decanone or farnesyl acetone. In each of thesecases, R₂ is H.

Preferred compounds of this invention include, but are not limited to:

1,1,1-trifluoro-7-octene-2,4-dione (ATFAC, allyltrifluoroacetoacetate),R₁ is CF₃, R₂ is H and R₃ is 1-butenyl, having the structure (enol form)##STR9##

1,1,1-trifluoro-8-methyl-7-nonene-2,4-dione (OTFAC,olefin-trifluoroacetoacetate), R₁ is CF₃, R₂ is H and R₃ is2-methyl-2-pentenyl, having the structure ##STR10##

1,1,1-trifluoro-5-prenyl-dodecane-2,4-dione (HOTFAC, heptylatedolefin-trifluoroacetoacetate), R₁ is CF₃, R₂ is H and R₃ is5-(2-methyl-2-dodecenyl), having the structure ##STR11##

1,1,1-trifluoro-8,12-dimethyl-trans-7,11-tridecadiene-2,4-dione (GTFAC,geranyltrifluoroacetoacetate), R₁ is CF₃, R₂ is H and R₃ is(E)-2,6-dimethyl-2,6-nonadienyl, having the structure ##STR12##

1,1,1-trifluoro-8,12-dimethyl-cis-7,11-tridecadiene-2,4-dione (NTFAC,neryltrifluoroactetoacetate), R₁ is CF₃, R₂ is H and R₃ is(Z)-2,6-dimethyl-2,6-nonadienyl, having the structure ##STR13##

and 1,1,1-trifluoro-8,12,16-trimethyl-7,11,15-heptadecatriene-2,4-dione(FTFAC, farnesyltrifluoroacetoacetate), R₁ is CF₃, R₂ is H and R₃ is2,6,10-trimethyl-2,6,10-tridecatrienyl (mixed EE, EZ, ZE and ZZisomers), having the structure ##STR14##

It will be understood that many of the compounds of this group contain aprenyl substituent and that compounds, containing a prenyl fragment,--CH₂ CH═C(CH₃)₂, are among preferred TFAC-derived diketones.

The TFAC-derived diketones are converted to corresponding M^(I) salts byreaction with a monovalent metal compound, preferably a compound ofCu^(I) or Ag^(I). It is preferred to use cuprous oxide, Cu₂ O, of veryhigh purity. It is most preferred to use Cu₂ O exceeding 99.9% purity.In order to obtain good yields of corresponding Cu^(I) -diketonecompounds, it is preferred to use about half an equivalent of Cu^(I)compound to TFAC-derived diketone. The structure of the monovalent metalsalts can be represented by the formula: ##STR15##

The M^(I) complexes of R₁ COCHR₂ COR₃ are useful as absorbents forcarbon monoxide and for hydrocarbons having at least oneolefinically-unsaturated bond. The Cu^(I) complexes are particularlypreferred for the absorption of carbon monoxide, olefins or acetylenesfrom feedstreams.

Solutions or slurries of the absorbent complexes in an organic solventare contacted with a stream containing carbon monoxide, an olefin or anacetylenic compound. The complexes bind carbon monoxide, the olefin orthe acetylenic compound. The complexes, containing bound carbonmonoxide, olefin or acetylenic compound, are isolated from the feedstream and further treated by heating or pressure reduction, or both, toliberate bound carbon monoxide, olefin or acetylenic compound. Thecomplexes of this invention therefore provide an effective means forremoval of carbon monoxide, olefins or acetylenic compounds from feedstreams.

Most preferred absorbent compounds are Cu^(I) complexes from1,1,1-trifluoro-8,12-dimethyl-trans-7,11-tridecadiene-2,4-dione (GTFAC)and from 1,1,1-trifluoro-8-methyl-7-nonene-2,4-dione (OTFAC). The M^(I)complexes are used for absorption of carbon monoxide or olefins in aninert organic solvent or diluent, particularly in ethylbenzene, toluene,cymene or the like.

An unexpected feature of the Cu^(I+-) R₁ COCR₂ COR₃ complexes is the lowheat of absorption, about -2 to -3 keal/mol. The complexes are thereforevery acceptable absorbents for carbon monoxide and olefins in feedstreams.

Other compounds of this invention, useful as absorbents for carbonmonoxide and olefins or other non-aromatic unsaturated hydrocarbons arethose derived from diketones of the formula ##STR16##

Compounds of this group can be made from a silver salt of aperfluorodiketone and an unsaturated halide, for example, allyl bromide.The following is typical of processes for making compounds of this type:##STR17##

The diketones can be converted to Cu^(I) or Ag^(I) complexes by the samemethods used for the TFAC-derived diketones. A most preferred compoundof this series is a compound in which R_(F') and R_(F") each aretrifluoromethyl and R is allyl. A most preferred metal derivative is theCu^(I) derivative.

BRIEF DESCRIPTION OF THE DRAWINGS

In FIG. 1 are shown Van't Hoff plots of equilibrium binding data fortypical Cu^(I) compounds and carbon monoxide or propylene.

BEST MODE FOR CARRYING OUT THE INVENTION

Most preferred diketones of the invention are1,1,1-trifluoro-7-octene-2,4-dione,1,1,1-trifluoro-8-methyl-7-nonene-2,4-dione,1,1,1-trifluoro-5-prenyl-do-decone-2,4-dione,1,1,1-trifluoro-8,12-dimethyl-cis (ortrans-)-7,11-tridecadiene-2,4-dione and1,1,1-trifluoro-8,12,16-trimethyl-7,11,15-heptadecatriene-2,4-dione.

Most preferred are Cu^(I) compounds derived from1,1,1-trifluoro-8,12-dimethyltrans-7,11-tridecadiene-2,4-dione,1,1,1-trifluoro-8-methyl-7-nonene-2,4-dione,1,1,1-trifluoro-5-prenyl-dodecane-2,4-dione or1,1,1-trifluoro-7-octene-2,4-dione.

Without further elaboration it is believed that one skilled in the artcan, using the preceding description, utilize the present invention toits fullest extent. The following preferred specific embodiments are,therefore, to be construed as merely illustrative and not limitative ofthe remainder of the disclosure in any way whatsoever.

In the following Examples, temperatures are set forth uncorrected indegrees Celsius or degrees Kelvin. Unless otherwise indicated, all partsand percentages are by weight.

5-Hexen-2-one, 6-methyl-5-hepten-2-one, ethyl trifluoroacetate,1,1,1,5,5,5-hexafluoro-2,4-pentanedione, nerolidol, and lithiumdiisopropylamide (solid) were obtained from Aldrich Chemical Co. (940West St. Paul Ave., Milwaukee, Wis. 53233). Geranyl acetone and nerylacetone were obtained from Fluka, Inc. (255 Oser Ave., Hauppauge, N. Y.11788). 6,10-Dimethyl-5,9-undecen-2-one (E and Z mixture) was obtainedfrom Wiley Co. (4654 Kenny Road, Columbus, Ohio 43220). Cuprous oxide(99.9%) was obtained from Cerac (407 North 13th St., Milwaukee, Wis.53233).

Solvents used are HPLC grade. Hexane and tetrahydrofuran (THF) aredistilled from calcium hydride under nitrogen. All operations in thepreparation of the free ligands or corresponding complexes are carriedout using standard Schlenk line techniques described by D. F. Shriver,"The Manipulation of Air-Sensitive Compounds," McGraw-Hill PublishingCo.

Farnesyl acetone is prepared from nerolidol by the method of Vorob'evaet al., Zhur. Obshchei Khim., vol. 29 (1959), pages 2314-2318,abstracted in Chem. Abs., vol. 54: 9987i.

Infrared spectra were obtained on a Perkin Elmer 684 spectrometer or aNicolet 20 SXB spectrometer. ¹ H NMR spectra were obtained using an IBMFY200 FT NRM spectrometer. Microananylses were performed by ResearchServices, Air Products & Chemicals, Inc. or Schwarzkopf MicroanalyticalLaboratory, Woodside, N. Y.

EXAMPLE 1 (a) Synthesis of Trifluoro-beta-diketone ligands of the TFAC(Trifluoroacetoacetate) Series

Derivatives of TFAC are obtained by reaction between ethyltrifluoroacetate and a ketone. Lithium diisopropylamide (LDA, 11.8 g,0.11 mol) is charged to a reaction flask, fitted with an additionfunnel, inlet for nitrogen and magnetic stirring bar under an atmosphereof dry nitrogen. Rubber septa are fitted into the flask and funnel. THF(300 mL) is added to the contents of the flask and a further 20 mL isplaced in the addition funnel. The ketone (0.1 mol) is charged to theaddition funnel and the contents of the flask are cooled to -78° C.using an isopropanol/dry ice slush bath. The ketone is added dropwise tothe stirred mixture over 20 min and stirring is continued at -78° C. for10 min or more, after which the dry ice slush bath is removed and theresulting enolate solution is allowed to warm up to room temperature.

Ethyl trifluoroacetate (6.0 mL, 0.1 mol) is added by a syringe over 5min, during which the reaction mixture darkens from a yellow color to areddish color. The resulting mixture is stirred overnight, after whichabout 80% of the THF is removed using a rotating evaporator. Theresulting concentrate is poured on to a 50/50 mixture of concentratedHCl/ice. The resulting mixture is extracted with three 100-mL portionsof petroleum ether. The combined petroleum ether extracts are washedwith three 100-mL portions of water, dried over anhydrous sodiumsulfate, filtered and evaporated. The products are obtained inquantitative yield and are about 99% pure.

NMR spectra, IR spectra and elemental analyses for thus-prepared TFACderivatives are given in Tables 1-3.

(b) Heptylation of OTFAC Ligand

6-Methyl-5-hepten-2-one (6.72 g, 0.052 mol) in 20 mL of THF is addedover 20 min to a solution of LDA (0.53 g, 0.05 mol) in 200 mL of THF at-78° C. as above. The resulting mixture is stirred at -78° C. for 10 minand then allowed to warm to room temperature.

Heptyl iodide (11.3 g, 0.05 mol) is added to this mixture and stirringis continued overnight at room temperature. The intermediate isprotonated by being poured over a 50/50 mixture of concentrated HCl/ice.The product is extracted into petroleum ether and isolated as above.

The crude reaction product is subjected to distillation under vacuum andthe fractions screened by IR spectroscopy for ketone content byabsorbance at about 1720 cm⁻¹. A fraction constituting 30% of thereaction product was found to be the desired ketone.

¹ H NMR, CD₂ Cl₂ : 0.83 ppm (t,3H); 1.25 ppm (bs,10H); 1.40 ppm (m, 2H);1.58 ppm (3, 3H); 1.68 ppm (s, 3H); 2.05 ppm (s, 3H); 2.15 ppm (m, 2H);2.4 ppm (m, 1H); 5.02 ppm (1H).

This ketone is subjected to reaction with ethyl trifluoroacetate asabove to produce HOTFAC ligand. The ligand is isolated by chelation withCu^(II), using aqueous cupric acetate solution, and eluted through acolumn of Davisil silica gel MPLC column, using hexane initially toremove impurities and then 50/50 methylene chloride/hexane to give theCu^(II) complex (91% purity). The Cu^(II) complex is treated with 200 mLof 6M HCl/methylene chloride (50:50 v/v) to liberate the free diketone.Characterization data for this compound are given in Tables 1-3.

                  TABLE 1                                                         ______________________________________                                        .sup.1 H NMR in CDCl.sub.3 for Trifluroacetoacetate (TFAC) Derivatives        Ligand     .sup.1 H NMR (δ)                                             ______________________________________                                        ATFAC      2.4 (t,2H); 2.55 (t,2H); 5.05(t,2H);                                          5.78(m,1H); 5.92(s,1H); 14.0(bs,1H)                                OTFAC      1.59(s,3H); 1.68(s,3H); 2.4(m,4H); 14.0(bs,1H)                     HOTFAC     0.9(t,3H); 1.25(s,10H); 1.6(s,5H); 1.66(s,3H);                                2.25(m,3H); 5.0(m,1H); 5.85(s,1H); 14.3(bs,1H)                     GTFAC      1.57(s,3H); 1.59(s,3H); 1.66(s,3H);                                           2.0(m,4H); 2.4(m,4H); 5.06(m,2H);                                             5.89(s,1H); 14.2(bs,1H)                                            NTFAC      1.58(s,3H); 1.66(s,6H); 2.02(d,4H);                                           2.39(m,4H); 5.06(t,2H); 5.88(s,1H); 14.5(bs,1H)                    FTFAC*     1.6(s, 6H); 1.7(s,6H); 2.0(d,8H); 2.4(m,4H);                                  5.1(t,3H); 5.9(s,1H); 12.5(bs,1H)                                  ______________________________________                                         *Mixture of regioisomers.                                                

                  TABLE 2                                                         ______________________________________                                        IR Spectra for TFAC Derivatives                                               (KBr plates, neat films)                                                      Ligand   IR                                                                   ______________________________________                                        ATFAC    3086.0(m), 2984.8(m), 2926.9(m), 1643.8(s), 1601.2(s),                        1448.9(m), 1419.7(m), 1366.7(m), 1282.8(s), 1203.3(s),                        1156.1(s), 1110.1(s), 995.35(m), 920.03(m),                                   868.72(m), 882.17(m) cm.sup.-1                                       OTFAC    2973.6(m), 2919.9(m), 2862.3(m), 1599.1(s),                                   1451.9(m), 1412.5(m), 1379.0(m), 1282.6(s),                                   1202.8(s), 1109.1(s), 875.28(m),                                              819.84(m), 796.14(m), 721.68(m) cm.sup.-1                            HOTFAC   2958.9(m), 2930.1(s), 2858.8(m), 1595.7(s),                                   1455.8(m), 1378.9(m), 1353.7(m), 1342.4(m),                                   1279.8(s), 1202.1(s), 1157.8(s), 1108.8(s), 886.63(m),                        801.39(m) cm.sup.-1                                                  GTFAC and                                                                              2960(m), 2905(m), 2850(m), 1590(s), 1450(m),                         NTFAC    1275(s), 1195(s), 1150(s), 875(m), 795(m) cm.sup.-1                  (identical)                                                                   FTFAC    2950(s), 2910(s), 2850(s), 1590(s), 1450(s),                                  1375(m), 1275(s), 1200(s), 1155(s), 1110(s), 880(m),                          830(m), 800(m) cm.sup.-1                                             ______________________________________                                    

                  TABLE 3                                                         ______________________________________                                        Elemental Analysis Data for TFAC Derivatives                                  ______________________________________                                        OTFAC         Calc'd for C.sub.10 H.sub.13 F.sub.3 O.sub.2 ;                                C 54.05; H 5.90; F 25.65; O 14.40                                             Found: C 54.17; H 6.1; F 24.50                                  ATFAC         Calc'd for C.sub.8 H.sub.9 F.sub.3 O.sub.2 :                                  C 49.49; H 4.67; F 29.36; O 16.48                                             Found: C 50.04; H 4.82; F 23.3                                  NTFAC         Calc'd for C.sub.15 H.sub.21 F.sub.3 O.sub.2 :                                C 62.05; H 7.29; F 19.63; O 11.02                                             Found: C 61.70; H 7.33                                          HOTFAC        Calc'd for C.sub.17 H.sub.23 F.sub.3 O.sub.2 :                                C 63.73; H 8.49; F 17.79; O 9.99                                              Found: C 64.04; H 8.40; F 13.3                                  FTFAC         Calc'd for C.sub.20 H.sub.24 F.sub.3 O.sub.2 :                                C 67.58; H 7.37                                                               Found: C 65.45; H 8.10                                          ______________________________________                                    

EXAMPLE 2

Preparation of Solid Cu^(I) Complexes of TFAC Ligands

One equivalent of free ligand is mixed with one half equivalent ofcuprous oxide under a nitrogen atmosphere. The period for reactionvaries from a few minutes (ATFAC) to a few hours (GTFAC), the end of thereaction being determined by solidification of the reaction mixture.HOTFAC does not produce a solid product after stirring overnight, butproduces a solid product upon addition of carbon monoxide to thereaction mixture.

The resulting solid product is broken up and washed with hexane until nofurther blue material (Cu^(II)) is leached out. Toluene is added to theresidue, using about 200 mL of toluene/g of solid, in a Schlenk flaskequipped with a rubber septum. Ethylene gas is bubbled into thesuspension for a few minutes under atmospheric pressure with stirring tosolubilize the Cu^(I) complex. During the process, the mixture becomesmore transparent and it is thought that the suspended solid is mostlycuprous oxide.

The resulting solution is filtered through celite (Aldrich Chemical Co.)to produce a faintly yellow solution, evaporation of which gives paleyellow pure crystalline Cu^(I) complex. If the product appears tocontain Cu^(II) complex by being colored with a blue tint, rinsing withhexane will remove this.

It appears that best yields of pure Cu^(I) complexes are obtained whenno more than one half equivalent of cuprous oxide is used and when thecuprous oxide is at least 99.9% pure. Use of higher amounts of cuprousoxides appears to encourage disproportionation to Cu^(II).

IR spectra, elemental analyses and NMR data for Cu^(I) complexes ofvarious TFAC ligands are given in Tables 4-6.

                  TABLE 4                                                         ______________________________________                                        IR Spectra for Cu.sup.I Complexes of TFAC Derivatives                         Cu.sup.I Complex                                                                        IR (KBr pellet)                                                     ______________________________________                                        Cu.sup.I GTFAC                                                                          2981.3(m), 2967.0(m), 2940.6(m), 2915.8(m),                                   2906.5(m), 2848.9(m), 1634.7(s), 1615.1(s),                                   1526.7(s), 1507.4(s), 1498.2(s), 1304.4(m),                                   1287.4(s), 1253.0(m), 1175.6(s), 1158.3(s),                                   1149.5(s), 1138.3(s), 848.89(m), 759.36(m) cm.sup.-1                Cu.sup.I OTFAC                                                                          2975(m), 2940(m), 2900(m), 1603(s), 1520(s),                                  1460(s), 1280(s), 1180(s), 1145(s), 1070(m),                                  790(m), 580(m) cm.sup.-1                                            Cu.sup.I HOTFAC                                                                         2910(s), 2850(m), 1609(s), 1590(sh), 1510(m),                                 1460(s), 1280(s), 1190(s), 1140(s), 1070(m),                                  800(m) cm.sup.-1                                                    Cu.sup.I ATFAC                                                                          2980(m), 2959(m), 2912(m), 1604(s), 1511(s),                                  1457(s), 1272(s), 1181(s), 1135(s) cm.sup.-1                        ______________________________________                                    

                  TABLE 5                                                         ______________________________________                                        Elemental Analyses for Cu.sup.I Complexes of TFAC Derivatives                 Cu.sup.I Complex                                                                        Analysis                                                            ______________________________________                                        Cu.sup.I OTFAC                                                                          Calc'd for C.sub.10 H.sub.12 F.sub.3 O.sub.2 Cu: C 42.18; H                   4.25; F 20.02;                                                                Cu 22.32. Found: C 42.28; H 4.23; F 18.89,                                    Cu 22.09                                                            Cu.sup.I ATFAC                                                                          Calc'd for C.sub.8 H.sub.8 F.sub.3 O.sub.2 Cu: C 37.43; H 3.14;               F 22.20;                                                                      Cu 24.76. Found: C 37.83; H 3.14; F 22.20;                                    Cu 24.60                                                            Cu.sup.I HOTFAC                                                                         Calc'd for C.sub.17 H.sub.26 F.sub.3 O.sub.2 Cu: C 53.32; H                   6.84; F 14.88;                                                                Cu 16.59. Found: C 55.68; H 7.20; F 17.95                           Cu.sup.I GTFAC                                                                          Calc'd for C.sub.15 H.sub.20 F.sub.3 O.sub.2 Cu: C 51.06; H                   5.71; F 16.15;                                                                Cu 18.01. Found: C 50.99; H 5.72; F 16.20;                                    Cu 20.82                                                            ______________________________________                                    

                  TABLE 6                                                         ______________________________________                                        .sup.1 H NMR Spectra for Cu.sup.I Complexes                                   Cu.sup.I Complex                                                                        .sup.1 H NMR                                                        ______________________________________                                        Cu.sup.I OTFAC                                                                          d.sub.8 toulene + ethylene (˜1 atm, 25° C.):                     1.55 ppm (d, 6H); 2.17 ppm (m, 4H); 4.2 ppm (s,                               6H)(ethylene), 5.05 ppm (m, 1H) (s, 1H); 5.8 ppm                              (s, 1H)                                                             Cu.sup.I ATFAC                                                                          d.sub.8 toulene + ethylene (˜1 atm, 25° C.):                     2.09 ppm (m, 4H); 4.05 ppm (s,˜3H)(ethylene);                           5.13 ppm (m, 1H); 5.75 ppm (s, 1H)                                  Cu.sup.I GTFAC                                                                          CDCl.sub.3 : 1.64 (s, 6H); 1.68 ppm (s, 3H); 2.17 ppm (s,                     4H); 2.28 ppm (t, 2H); 2.37 ppm (d, 2H); 4.95 ppm                             (m, 2H); 5.57 ppm (s, 1H)                                           ______________________________________                                    

EXAMPLE 3 Volumetric Gas Uptake Measurements for Cu^(I) TFAC Complexes

Volumetric gas uptake measurements are carried out in a glass apparatusprovided with carbon monoxide and propylene feeds, metered throughmercury bubblers, operatively connected to a vacuum line and to mercurygas burets for measuring gas volume changes, connected to a pressuretransducer (MKS 1000 torr) for measuring absolute pressure readings andto a thermostatted sample chamber. In normal operation, the apparatuspermitted measuring volume changes of ±0.007 cm³, with errors inpressure and bath temperature of ±0.1 torr and ±0.2° C., respectively.The apparatus, other than the sample chamber, was not thermostatted, andwas exposed to ambient temperature variations of ±0.5° C. during thecourse of a run. The sample of complex is sealed in a glass vial,containing sand and having a magnet sealed therein. Volume changes from1-50 cm³ at pressures of 50-1000 torr and temperatures of 40° C. to -50°C. could be measured using the apparatus.

In a representative run, 50-200 mg of sample is sealed in a break sealvial under 75-600 torr of the selected uptake gas. Sand is charged tothe vial to minimize dead volume. A glass-encased magnetic stirring baris attached to the break vial. The resulting sample is placed in asample chamber (uptake flask) and the contents of the flask aredegassed. Dry distilled ethylbenzene is added to the sample chamberusing a syringe. The uptake flask is attached to the volumetricapparatus and the system is evacuated. The sample vial is suspendedabove the ethylbenzene, using an external magnet, and the ethylbenzeneis stirred rapidly. The flask is immersed in a constant temperature bath(-25° C. to 40° C.) and brought to temperature. Ethylbenzene vaporpressure is allowed to equilibrate throughout the system. Upon reachingequilibrium (1-2 h), the pressure is recorded. The system is pressurizedwith uptake gas until the total pressure equals ethylbenzene vaporpressure plus pressure of uptake gas in the break vial. The system isallowed to come to equilibrium for 1.5-2.5 h with pressure adjustmentsto maintain the correct total pressure.

The gas buret is isolated and mercury levels in the buret columns, totalpressure, room temperature and bath temperature are recorded. The breakvial is dropped and broken to initiate gas uptake. Mercury levels of thegas buret are adjusted at 5-10 min intervals to bring total pressureback to the initially-measured total pressure.

After each adjustment, reaction time, total pressure, mercury levels androom and bath temperatures are recorded. Adjustments are made until nochange in either mercury levels or total pressure is observed for 20-30min. The measured change in mercury levels permits calculation of volumechange, which in turn is related to moles of uptake gas absorbed. Theequilibrium constant is calculated from molar uptake, total moles ofcomplex and pressure of uptake gas.

Results for absorption of CO by Cu^(I) OTFAC are given in Table 7.Results for reversible absorption of CO by Cu^(I) GTFAC are shown inTable 8. In Table 9 are shown results of experiments on reversibleabsorption of propylene by Cu^(I) GTFAC.

These experiments show that Cu^(I) TFAC derivatives of this inventionfunction as absorbents for carbon monoxide and for olefins. The resultsin Tables 7-9 are also shown in FIG. 1.

Other binding parameters for the complexes of this invention arecalculated. The equilibrium constant is shown in terms of P_(1/2) (gas),which is the pressure (in torr) of the gas, required for reaction ofhalf of the complex. As shown in Table 10, the heat of binding for bothCO and propylene is very low, about 2-3 kcal/mol. This low heat ofbinding means that attainment of the maximum (equilibrium) capacity ofthe absorbent system is favored. The complexes of this invention have asignificantly lower heat of binding than the Cosorb cuproustetrachloroaluminate tolene complexes in commercial use, as furthershown in Table 10.

Example 4 (a) Synthesis of1,1,1-Trifluoro-3-trifluoroacetyl-5-hexene-2-one(Allylhexafluoroacetylacetone)

To a Schlenk tube equipped with a septum and stirring bar is chargedsilver oxide (6.13 g, 0.026 mol). The tube is degassed. Diethyl ether(60 mL) is added by a cannula and the mixture is stirred to produce ablack suspension. Hexafluoroacetylacetone (7.2 mL, 0.051 mol) is slowlyadded from a syringe over 15 min, during which an exotherm is observed.The resulting mixture is stirred for 1.5 h and then filtered throughdiatomaceous earth on a medium porosity Schlenk frit to give a slightlyyellow solution. Solids on the filter are washed with diethyl ether(three 20-mL portions). The combined filtrate and washings areevaporated under vacuum to leave an off-white solid.

                                      TABLE 7                                     __________________________________________________________________________    Reversible CO Absorption Data for Cu.sup.I OTFAC in Ethylbenzene              [Cu].sup.T (M)                                                                       P.sub.CO (torr)                                                                    % Cu(CO)                                                                            K.sub.eq (torr.sup.-1)                                                                  T(K)                                                                             -lnK.sub.eq                                                                        1/T(K.sup.-1)                             __________________________________________________________________________    1.77 × 10.sup.-2                                                               191.1                                                                              46.2   4.5 ± 0.1  × 10.sup.-3                                                        254.2                                                                            5.40 3.93 × 10.sup.-3                    1.94 × 10.sup.-2                                                               373.0                                                                              53.5  3.09 ± 0.06 × 10.sup.-3                                                        275.8                                                                            5.78 3.62 × 10.sup.-3                    2.33 × 10.sup.-2                                                               276.9                                                                              40.5  2.46 ± 0.06 × 10.sup.-3                                                        295.2                                                                            6.00 3.39 × 10.sup.-3                    1.12 × 10.sup.-2                                                               158.5                                                                              24.5  2.05 ± 0.06 × 10.sup.-3                                                        310.2                                                                            6.19 3.22 × 10.sup.-3                    __________________________________________________________________________     ##STR18##                                                                     ##STR19##                                                                

                                      TABLE 8                                     __________________________________________________________________________    Reversible CO Absorption Data for Cu.sup.I GTFAC in Ethylbenzene              [Cu].sup.T (M)                                                                       P.sub.CO (torr)                                                                    % Cu(CO)                                                                            K.sub.eq (torr.sup.-1)                                                                  T(K)                                                                             -lnK.sub.eq                                                                        1/T(K.sup.-1)                             __________________________________________________________________________    1.77 × 10.sup.-2                                                               183.7                                                                              75.6  1.68 ± 0.07 × 10.sup.-2                                                        253.2                                                                            4.08 3.95 × 10.sup.-3                    1.97 × 10.sup.-2                                                               107.3                                                                              57.8  1.28 ± 0.03 × 10.sup.-2                                                        276.2                                                                            4.36 3.62 × 10.sup.-3                    1.17 × 10.sup.-2                                                                80.8                                                                              44.4  0.99 ± 0.03 × 10.sup.-2                                                        295.0                                                                            4.62 3.39 × 10.sup.-3                    1.30 × 10.sup.-2                                                               240.0                                                                              70.1  0.79 ± 0.03 × 10.sup.-2                                                        309.2                                                                            4.84 3.23 × 10.sup.-3                    __________________________________________________________________________     ##STR20##                                                                     ##STR21##                                                                

                                      TABLE 9                                     __________________________________________________________________________    Reversible Propylene Absorption Data for Cu.sup.I GTFAC in Ethylbenzene              PC.sub.3 H.sub.6                                                                  % Cu                                                               [Cu].sup.T (M)                                                                       (torr)                                                                            (C.sub.3 H.sub.6)                                                                 K.sub.eq (torr.sup.-1)                                                                  T(K)                                                                             -lnK.sub.eq                                                                        1/T(K.sup.-1)                                __________________________________________________________________________    1.82 × 10.sup.-2                                                               106.3                                                                             77.4                                                                               3.2 ± 0.3  × 10.sup.-2                                                        263.2                                                                            3.45 3.80 × 10.sup.-3                       2.27 × 10.sup.-2                                                                99.9                                                                             73.0                                                                               2.7 ± 0.1 × 10.sup.-2                                                         275.5                                                                            3.61 3.63 × 10.sup.-3                       1.43 × 10.sup.-2                                                               136.3                                                                             72.6                                                                              1.94 ± 0.08 × 10.sup.-2                                                        294.0                                                                            3.94 3.40 × 10.sup.-3                       1.76 × 10.sup.-2                                                               213.3                                                                             75.4                                                                              1.44 ± 0.05 × 10.sup.-2                                                        312.0                                                                            4.24 3.20 × 10.sup.-3                       4.89 × 10.sup.-2                                                               577.3                                                                             90.6                                                                              1.67 ± 0.08 × 10.sup.-2                                                        291.5                                                                            4.09 3.43 × 10.sup.-3                       __________________________________________________________________________     ##STR22##                                                                     ##STR23##                                                                

                  TABLE 10                                                        ______________________________________                                        Gas Uptake Parameters in Ethylbenzene                                                            P.sub.1/2 ΔH                                         Complex     Gas    (torr)    (kcal/mol at 295° K.)                     ______________________________________                                        Cosorb      CO      79       -6                                               Cu.sup.I OTFAC                                                                            CO     402       -2.2 ± 0.2                                    Cu.sup.I GTFAC                                                                            CO     101       -2.1 ± 0.2                                    Cu.sup.I GTFAC                                                                            C.sub.3 H.sub.6                                                                       52       -2.6 ± 0.2                                    ______________________________________                                    

The solid is redissolved in 60 mL of diethyl ether and the resultingsolution is cooled to -78° C. in a dry ice-isopropanol bath. To anaddition funnel is charged diethyl ether (20 mL) and allylbromide (4.4mL, 0.051 mol). This solution is added dropwise to the cold solution ofsilver hexafluoroacetylacetate. After about half the allyl bromide isadded, a precipitate is formed in the reaction vessel. After all theallyl bromide is added, the reaction mixture is allowed to warm to roomtemperature under a stream of nitrogen. The product is filtered underambient conditions to remove precipitated silver bromide. The solids onthe filter are washed with three 50-mL portions of diethyl ether. Thecombined filtrate and washings are evaporated on a rotating evaporatorto a volume of about 125 mL. The remaining material is distilled undernitrogen. The highest boiling fraction (108° C./760 torr) is identifiedas allylhexafluoroacetylacetone. The yield is 6.38 g (0.026 mol, 51%).

Anal. Calc'd for C₈ H₆ F₆ O₂ : C 38.73; H 2.44. Found: C 38.75, 38.62; H2.44, 2.47.

IR (neat film): C═O, 1779 (s) and 1753 (s) cm⁻¹ ; C═C, 1642 (w) cm⁻¹.

¹ H NMR (in CDCl₃): 2.74 ppm(t, 2H); 4.51 ppm (t, 1H); 5.16 ppm (m, 2H);5.68 ppm (m, 1H) δ TMS.

(b) Preparation of Cu^(I) Allylhexafluoroacetylacetonate

Allyl hexafluoroacetylacetonate (AHFAC) is reacted with Cu₂ O as inExample 2 to a give a solid product. The Cu^(I) complex is isolated asin Example 2, in the form of a pale yellow powder, which binds bothethylene and CO reversibly in toluene solution. However, Cu^(I) AFHAC isinsoluble in toluene until CO or ethylene is added to the system.

We claim:
 1. A compound of the formula ##STR24## wherein R₁ istrichloromethyl or R_(F) ; R_(F) is C_(n) F_(2n+l) and n is 1-8; R₂ is Hor hydrocarbyl of 2-20 carbon atoms having from one to three olefinicunsaturated bonds; R₃ is hydrocarbyl of 2-20 carbon atoms having fromone to three olefinic unsaturated bonds and M^(I) is Cu^(I) or Ag^(I).2. A compound of claim 1, wherein M^(I) is Cu^(I), R₁ is R_(F) and R₂ isH.
 3. A compound of claim 1, wherein M^(I) is Cu^(I), R₁ is CF₃ and R₂is H.
 4. A compound of claim 1, wherein M^(I) is Cu^(I), R₁ is CF₃ andR₃ is 2-butenyl, 2-methyl-2-pentenyl, (E)-2,6-dimethyl-2,6-nonadienyl or5-(2-methyl-2-dodecenyl).
 5. Copper (I)1,1,1,-trifluoro-8,12-dimethyl-trans-7,11-tridecadiene-2,4-dioneate, acompound of claim
 1. 6. Copper(I)1,1,1-trifluoro-8-methyl-7-nonene-2,4-dioneate, a compound of claim 1.7. Copper(I) 1,1,1-trifluoro-5-prenyl-dodecane-2,4-dioneate, a compoundof claim
 1. 8. Copper(I) 1,1,1-trifluoro-7-octene-2,4-dioneate, acompound of claim
 1. 9. A compound of the formula ##STR25## whereinR_(F') and R_(F") are independently selected from perfluoroalkyl of 1-8carbon atoms; R is hydrocarbyl of 2-20 carbon atoms having from one tothree olefinic unsaturated bonds and M^(I) is Cu^(I) or Ag^(I).